CN104445575A - Deep oxidation treatment method of steroid hormone drug wastewater - Google Patents
Deep oxidation treatment method of steroid hormone drug wastewater Download PDFInfo
- Publication number
- CN104445575A CN104445575A CN201410749247.3A CN201410749247A CN104445575A CN 104445575 A CN104445575 A CN 104445575A CN 201410749247 A CN201410749247 A CN 201410749247A CN 104445575 A CN104445575 A CN 104445575A
- Authority
- CN
- China
- Prior art keywords
- gac
- steroid hormone
- doped
- water
- cod
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002351 wastewater Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000003270 steroid hormone Substances 0.000 title claims abstract description 24
- 239000003814 drug Substances 0.000 title claims abstract description 22
- 230000003647 oxidation Effects 0.000 title claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 19
- 229940079593 drug Drugs 0.000 title abstract 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 230000015556 catabolic process Effects 0.000 claims abstract description 20
- 238000006731 degradation reaction Methods 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 13
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 238000005070 sampling Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 150000002978 peroxides Chemical class 0.000 claims description 7
- 238000010168 coupling process Methods 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 238000009303 advanced oxidation process reaction Methods 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical class O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241001274216 Naso Species 0.000 description 1
- 101710171243 Peroxidase 10 Proteins 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical class O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002124 endocrine Effects 0.000 description 1
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
- C02F1/766—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/026—Treating water for medical or cosmetic purposes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to a deep oxidation treatment method of steroid hormone drug wastewater, and belongs to the technical field of wastewater treatment. According to the deep oxidation treatment method, a current catalyst is used for the deep treatment process of the steroid hormone drug wastewater and carries out the degradation treatment on the steroid hormone drug wastewater by being matched with a multiple-oxidizing agent combining technology. Compared with a general deep oxidation treatment method, the deep oxidation treatment method of the steroid hormone drug wastewater, which is disclosed by the invention, can be used for enhancing the COD removal ratio by more than 50% and solving the problem that effluent water is difficult to degrade after the steroid hormone drug wastewater is subjected to biochemical treatment, thereby having the advantages of simplicity, low cost, good degradation effect and higher practical value.
Description
Technical field
The present invention relates to a kind of deep oxidation treatment process of steroid hormone medicine waste water, belong to the technical field of wastewater treatment.
Background technology
Steroid hormone medicine waste water is through pretreatment stage and biochemical treatment stage, and chemical oxygen demand (COD) (COD) clearance of waste water can reach higher level, but water outlet COD is still difficult to reach emission standard.In view of steroid hormone class waste water will demonstrate the effect of stronger disturbance endocrine under extremely low concentration conditions, the potential hazard of this kind of Wastewater on Ecological Environmental and human health can not be ignored.Therefore, the research that the steroid hormone class waste water below standard to COD after this kind of process premenstruum carries out deep oxidation process is very important, to destroy the structure of residual steroid hormone medicine, eliminates the harm of Wastewater on Ecological Environmental and human health.
Treatment of Organic Wastewater by Advanced Oxidation Processes is the new technology of wastewater treatment both at home and abroad at present, mainly under the effect of composite oxidant, rayed, electricity or catalyzer etc., bring out intermediate material (hydroxyl radical free radical OH, the peroxide HO with strong oxidizing property that produce various ways
2deng), oxidation capacity is extremely strong, almost reacts with any organic pollutant in waste water, and can bring out chain reaction as initiator, and pollutent is carbonic acid gas, water or mineral salt by exhaustive oxidation, and does not produce new pollutent.In recent years, countries in the world government to environment protection pay attention to day by day, thus accelerates the development & application of advanced oxidation processes.Advanced oxidation processes the organic pollutant of biological degradation or difficult for biological degradation can will can not be oxidized to small organic molecule, and oxidation step of going forward side by side is removed.Roundup (" water technology ", 2013,39,114-116 is had at present by the research of advanced oxidation processes process waste water; " Environ.Sci.Technol. " 2011,45,3665 – 3671), Liu Zhifeng etc. report a kind of research (" Chemical Engineering Technology and exploitation " of advanced oxidation processes Treatment of Wastewater in Coking, 2012,41,41-43), Feng Xiaojing reports deep oxidation process pulp-making waste-water (" Chinese paper industry ", 2009,30,1-7), but research steroid hormone medicine waste water being carried out to deep oxidation process is less, and what have practical value has no report substantially.
Nano-TiO
2photocatalyst, because having high reactivity, furthermore has central hole structure, and physico-chemical property is stable waits good characteristic, and can be used for the catalyzed degradation of pollutent, be the focus that people study as advanced oxidation processes always.Due to anatase titanium dioxide TiO
2up to 3.2eV energy level difference, make TiO
2nanoparticle can only utilize the energy of 3-5% in daylight.The doping of metal and non-metallic element element is that one simply, effectively modifies TiO
2method.It not only can make TiO
2active region moves on to visible region by ultraviolet, can also effectively prevent electronics and hole to reunite.The TiO of doping
2in visible region, photocatalysis effect increases, as document (Ceram.Int.2009,3061 – 3065) is mentioned: under LED visible light environment, and doping 0.8%NaSO
4s doping-TiO
2degraded tropeolin-D, after 5h, methyl orange degradation rate reaches 95%, far above 5% degradation rate of P25 under same environment.But the TiO of doping
2not easily reclaim in actual use, its cost is higher, is difficult to scale and uses.And oxygenant such as hydrogen peroxide, clorox etc. conventional in enterprise's sewage disposal has good effect when disposing of sewage on a large scale, but for the lower bio-chemical effluent of COD, the COD clearance of these oxygenants is scarcely more than 50%.Therefore, if by doped Ti O
2degraded thoroughness with can combine by the oxygenant such as hydrogen peroxide, clorox that uses of scale, develop a kind of scale can use and can have again the high-level oxidation technology of better COD clearance, have the method for better COD clearance to be urgent hope at present for the singularity of pollutent structure contained by steroid hormone medicine waste water.Based on above-mentioned factor, the invention discloses and a kind ofly coordinate multiple oxygenant coupling technique to carry out the deep oxidation treatment process of steroid hormone medicine waste water from controlling catalyst.
Summary of the invention
The present invention essentially discloses a kind of deep oxidation treatment process of steroid hormone medicine waste water, it is characterized in that using from controlling catalyst in the advanced treatment process of steroid hormone medicine waste water, and coordinate multiple oxygenant coupling technique to carry out the degradation treatment of steroid hormone medicine waste water, the step of employing is as follows:
(1) preparation of catalyzer: under condition of ice bath, first by TiCl
4dropwise add in frozen water, then to add with titanium source mol ratio be the FeCl of 1 ~ 3%
36H
2o, reflux, ageing, by centrifugal for the faint yellow material obtained, roasting 2 ~ 4h at a certain temperature after washing and drying, obtains Fe doped Ti O
2.By appropriate Fe doped Ti O
2be placed in water mix and blend 1 ~ 3h with Φ 2 gac, after filtration, Fe doped Ti O will be adsorbed
2gac dry.
(2) catalyzed degradation: get above-mentioned obtained gac and join in 1000mL flask in right amount, get pH value be 2 COD be that the 400mL bio-chemical effluent water sample of 360mg/L joins in 1000mL flask, quantitatively pipette or pass into two or more oxygenant in 1000mL flask, it is 0.06mol/L (ozone is by oxygen amount metering conversion of living) that oxygenant adds total amount, stir 20 ~ 60min, reaction terminates rear filtering gac, and water sampling surveys COD, calculates the clearance of COD.The measuring method of COD all adopts potassium dichromate process (GB11914-89).
Below be namely the deep oxidation treatment process of a kind of steroid hormone medicine waste water disclosed in this invention.In step of the present invention (1), during catalyst preparing, maturing temperature is 350 ~ 550 DEG C, Fe doped Ti O
2be 1:20 ~ 1:100 with the mass ratio of Φ 2 gac; In step (2), catalyst activity charcoal consumption is 1 ~ 5% of the actual degraded water yield; Step (2) oxygenant should select dioxide peroxide, ozone, clorox, hydrogen peroxide etc. two or more, the add-on of each oxygenant is identical, add total amount be 0.06mol/L (ozone by live oxygen amount metering conversion); The gac leaching gac in step (2) is reusable.
The invention has the beneficial effects as follows and employ a kind of homemade catalyzer, and in conjunction with the coupling of multiple oxygenant, solve the problem of the water outlet difficult degradation after the process of steroid hormone medicine wastewater biochemical, homemade catalyzer is reusable, make that the deep oxidation treatment process of steroid hormone medicine waste water is simple, cost is low, good degrading effect, there is larger practical value.
Embodiment
Further illustrate flesh and blood of the present invention with example below, but they are not construed as limiting the invention.
Embodiment 1:
(1) preparation of catalyzer: under condition of ice bath, first by TiCl
4dropwise add in frozen water, then to add with titanium source mol ratio be the FeCl of 1%
36H
2o, reflux 4h, ageing 2h, then by centrifugal for the faint yellow material obtained, in 80 DEG C of oven dry after washing, then roasting 3h at 450 DEG C, obtains Fe doped Ti O
2.By 0.3g Fe doped Ti O
2be placed in 100mL water mix and blend 1h with 6g Φ 2 gac, after filtration, Fe doped Ti O will be adsorbed
2gac in 80 DEG C of oven dry.
(2) catalyzed degradation: get above-mentioned obtained gac 4g and join in 1000mL flask, get pH value be 2 COD be that the 400mL bio-chemical effluent water sample of 360mg/L joins in 1000mL flask, quantitatively add dioxide peroxide and each 0.02mol of clorox in 1000mL flask, it is 0.06mol/L that oxygenant adds total amount, stir 60min, reaction terminates rear filtering gac, and the clearance that water sampling surveys COD, COD is 76.4%.
Embodiment 2:
(1) preparation of catalyzer: under condition of ice bath, first by TiCl
4dropwise add in frozen water, then to add with titanium source mol ratio be the FeCl of 2%
36H
2o, reflux 4h, ageing 2h, then by centrifugal for the faint yellow material obtained, in 80 DEG C of oven dry after washing, then roasting 2h at 550 DEG C, obtains Fe doped Ti O
2.By 0.3g Fe doped Ti O
2be placed in 100mL water mix and blend 1h with 12g Φ 2 gac, after filtration, Fe doped Ti O will be adsorbed
2gac in 80 DEG C of oven dry.
(2) catalyzed degradation: get above-mentioned obtained gac 10g and join in 1000mL flask, get pH value be 2 COD be that the 400mL bio-chemical effluent water sample of 360mg/L joins in 1000mL flask, add dioxide peroxide 0.03mmol and pass into ozone in 1000mL flask, it is 0.06mol/L (ozone is by oxygen amount metering conversion of living) that oxygenant adds total amount, stir 40min, reaction terminates rear filtering gac, and the clearance that water sampling surveys COD, COD is 88.6%.
Embodiment 3:
(1) preparation of catalyzer: under condition of ice bath, first by TiCl
4dropwise add in frozen water, then to add with titanium source mol ratio be the FeCl of 3%
36H
2o, reflux 4h, ageing 2h, then by centrifugal for the faint yellow material obtained, in 80 DEG C of oven dry after washing, then roasting 3h at 350 DEG C, obtains Fe doped Ti O
2.By 0.3g Fe doped Ti O
2be placed in 100mL water mix and blend 3h with 30g Φ 2 gac, after filtration, Fe doped Ti O will be adsorbed
2gac in 80 DEG C of oven dry.
(2) catalyzed degradation: get above-mentioned obtained gac 20g and join in 1000mL flask, get pH value be 2 COD be that the 400mL bio-chemical effluent water sample of 360mg/L joins in 1000mL flask, quantitatively add dioxide peroxide and each 0.02mol of hydrogen peroxide in 1000mL flask, it is 0.06mol/L that oxygenant adds total amount, stir 50min, reaction terminates rear filtering gac, and the clearance that water sampling surveys COD, COD is 82.7%.
(3) catalyzer is reused: in 80 DEG C of oven dry after gac water previous step leached rinses, repeat above-mentioned steps (2), the clearance of COD is 82.0%.Catalyzer is reused 2 times again, and the clearance of COD is respectively 81.6% and 81.0%.
Embodiment 4:
(1) preparation of catalyzer: under condition of ice bath, first by TiCl
4dropwise add in frozen water, then to add with titanium source mol ratio be the FeCl of 2%
36H
2o, reflux 4h, ageing 2h, then by centrifugal for the faint yellow material obtained, in 80 DEG C of oven dry after washing, then roasting 3h at 450 DEG C, obtains Fe doped Ti O
2.By 0.3g Fe doped Ti O
2be placed in 100mL water mix and blend 3h with 24g Φ 2 gac, after filtration, Fe doped Ti O will be adsorbed
2gac in 80 DEG C of oven dry.
(2) catalyzed degradation: get above-mentioned obtained gac 16g and join in 1000mL flask, get pH value be 2 COD be that the 400mL bio-chemical effluent water sample of 360mg/L joins in 1000mL flask, quantitatively add dioxide peroxide, clorox, each 0.02mol of hydrogen peroxide in 1000mL flask, it is 0.06mol/L that oxygenant adds total amount, stir 20min, reaction terminates rear filtering gac, and the clearance that water sampling surveys COD, COD is 79.8%.
(3) catalyzer is reused: in 80 DEG C of oven dry after gac water previous step leached rinses, repeat above-mentioned steps (2), the clearance of COD is 79.0%.Catalyzer is reused 2 times again, and the clearance of COD is respectively 78.5% and 78.1%.
Embodiment 5:
(1) preparation of catalyzer: under condition of ice bath, first by TiCl
4dropwise add in frozen water, then to add with titanium source mol ratio be the FeCl of 3%
36H
2o, reflux 4h, ageing 2h, then by centrifugal for the faint yellow material obtained, in 80 DEG C of oven dry after washing, then roasting 4h at 350 DEG C, obtains Fe doped Ti O
2.By 0.3g Fe doped Ti O
2be placed in 100mL water mix and blend 2h with 16g Φ 2 gac, after filtration, Fe doped Ti O will be adsorbed
2gac in 80 DEG C of oven dry.
(2) catalyzed degradation: get above-mentioned obtained gac 12g and join in 1000mL flask, get pH value be 2 COD be that the 400mL bio-chemical effluent water sample of 360mg/L joins in 1000mL flask, add clorox and each 0.03mol of hydrogen peroxide in 1000mL flask, it is 0.06mol/L that oxygenant adds total amount, stir 40min, reaction terminates rear filtering gac, and the clearance that water sampling surveys COD, COD is 71.0%.
Embodiment 6:
(1) preparation of catalyzer: under condition of ice bath, first by TiCl
4dropwise add in frozen water, then to add with titanium source mol ratio be the FeCl of 1%
36H
2o, reflux 4h, ageing 2h, then by centrifugal for the faint yellow material obtained, in 80 DEG C of oven dry after washing, then roasting 2h at 550 DEG C, obtains Fe doped Ti O
2.By 0.3g Fe doped Ti O
2be placed in 100mL water mix and blend 2h with 12g Φ 2 gac, after filtration, Fe doped Ti O will be adsorbed
2gac in 80 DEG C of oven dry.
(2) catalyzed degradation: get above-mentioned obtained gac 8g and join in 1000mL flask, get pH value be 2 COD be that the 400mL bio-chemical effluent water sample of 360mg/L joins in 1000mL flask, add clorox and each 0.02mol of hydrogen peroxide in 1000mL flask, and pass into ozone in 1000mL flask, it is 0.06mol/L (ozone is by oxygen amount metering conversion of living) that oxygenant adds total amount, stir 30min, reaction terminates rear filtering gac, the clearance that water sampling surveys COD, COD is 86.4%.
Embodiment 7:
(1) preparation of catalyzer: under condition of ice bath, first by TiCl
4dropwise add in frozen water, then to add with titanium source mol ratio be the FeCl of 1%
36H
2o, reflux 4h, ageing 2h, then by centrifugal for the faint yellow material obtained, in 80 DEG C of oven dry after washing, then roasting 2h at 450 DEG C, obtains Fe doped Ti O
2.By 0.3g Fe doped Ti O
2be placed in 100mL water mix and blend 2h with 12g Φ 2 gac, after filtration, Fe doped Ti O will be adsorbed
2gac in 80 DEG C of oven dry.
(2) catalyzed degradation: get above-mentioned obtained gac 10g and join in 1000mL flask, get pH value be 2 COD be that the 400mL bio-chemical effluent water sample of 360mg/L joins in 1000mL flask, add clorox and each 0.02mol of hydrogen peroxide in 1000mL flask, and pass into ozone in 1000mL flask, it is 0.06mol/L (ozone is by oxygen amount metering conversion of living) that oxygenant adds total amount, stir 30min, reaction terminates rear filtering gac, the clearance that water sampling surveys COD, COD is 77.4%.
Embodiment 8:
(1) preparation of catalyzer: under condition of ice bath, first by TiCl
4dropwise add in frozen water, then to add with titanium source mol ratio be the FeCl of 1%
36H
2o, reflux 4h, ageing 2h, then by centrifugal for the faint yellow material obtained, in 80 DEG C of oven dry after washing, then roasting 2h at 450 DEG C, obtains Fe doped Ti O
2.By 0.3g Fe doped Ti O
2be placed in 100mL water mix and blend 2h with 12g Φ 2 gac, after filtration, Fe doped Ti O will be adsorbed
2gac in 80 DEG C of oven dry.
(2) catalyzed degradation: get above-mentioned obtained gac 10g and join in 1000mL flask, get pH value be 2 COD be that the 400mL bio-chemical effluent water sample of 360mg/L joins in 1000mL flask, add hydrogen peroxidase 10 .06mol in 1000mL flask, and pass into ozone in 1000mL flask, it is 0.06mol/L that oxygenant adds total amount, stirs 30min, and reaction terminates rear filtering gac, the clearance that water sampling surveys COD, COD is 58.2%.
Claims (4)
1. the deep oxidation treatment process of a steroid hormone medicine waste water, it is characterized in that in the advanced treatment process of steroid hormone medicine waste water, use existing controlling catalyst, and coordinate multiple oxygenant coupling technique to carry out the degradation treatment of steroid hormone medicine waste water, the step of employing is as follows:
(1) preparation of catalyzer: under condition of ice bath, first by TiCl
4dropwise add in frozen water, then to add with titanium source mol ratio be the FeCl of 1 ~ 3%
36H
2o, reflux, ageing, by centrifugal for the faint yellow material obtained, at 350 ~ 550 DEG C of roasting 2 ~ 4h after washing and drying, obtains Fe doped Ti O
2, by appropriate Fe doped Ti O
2be placed in water mix and blend 1 ~ 3h with Φ 2 gac, after filtration, Fe doped Ti O will be adsorbed
2gac dry;
(2) catalyzed degradation: get above-mentioned obtained gac and join in 1000mL flask in right amount, get pH value be 2 400mL bio-chemical effluent water sample join in flask, quantitatively pipette or pass into two or more oxygenant in flask, it is 0.06mol/L (ozone is by oxygen amount metering conversion of living) that oxygenant adds total amount, stir 20 ~ 60min, reaction terminates rear filtering gac, and water sampling surveys COD, calculates the clearance of COD.
2. method according to claim 1, is characterized in that Fe doped Ti O in step (1)
2be 1:20 ~ 1:100 with the mass ratio of Φ 2 gac.
3. method according to claim 1, is characterized in that " the absorption Fe doped Ti O of catalyzer in step (2)
2gac " consumption is 1 ~ 5% of the water yield of need degrading, reusable more than 3 times of this catalyzer.
4. method according to claim 1, is characterized in that oxygenant in step (2) is dioxide peroxide, ozone, clorox, hydrogen peroxide wherein 2 ~ 3 kinds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410749247.3A CN104445575B (en) | 2014-12-09 | 2014-12-09 | A kind of deep oxidation treatment process of steroid hormone medicine waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410749247.3A CN104445575B (en) | 2014-12-09 | 2014-12-09 | A kind of deep oxidation treatment process of steroid hormone medicine waste water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104445575A true CN104445575A (en) | 2015-03-25 |
| CN104445575B CN104445575B (en) | 2016-04-20 |
Family
ID=52892434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410749247.3A Expired - Fee Related CN104445575B (en) | 2014-12-09 | 2014-12-09 | A kind of deep oxidation treatment process of steroid hormone medicine waste water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104445575B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106800321A (en) * | 2015-11-25 | 2017-06-06 | 湖南恒光化工有限公司 | A kind of process units that can process waste water |
| CN108017223A (en) * | 2016-11-03 | 2018-05-11 | 浙江水美环保工程有限公司 | A kind of steroid pharmacy wastewater treatment method |
| CN109368859A (en) * | 2018-11-15 | 2019-02-22 | 河南利华制药有限公司 | Upper fluorine waste water zero discharge treatment process in steroidal drug production |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1899686A (en) * | 2006-07-24 | 2007-01-24 | 同济大学 | Process for preparing iron blended TiO2/active carbon composite visible light catalyst |
| CN101219371A (en) * | 2007-01-08 | 2008-07-16 | 北京化工大学 | Photocatalysis oxidation treated high concentration organic trade waste |
| CN101565219A (en) * | 2008-04-25 | 2009-10-28 | 北京化工大学 | Process for photocatalytic treatment of industrial waste water |
| CN101628236A (en) * | 2009-08-03 | 2010-01-20 | 浙江理工大学 | Preparation method of kieselguhr load type compound photocatalyst with iron ions doped titanium dioxide |
| CN101905154A (en) * | 2010-08-20 | 2010-12-08 | 中国林业科学研究院林产化学工业研究所 | Method for improving efficiency of visible light response doping-type M-TiO2/AC photocatalyst |
| CN101920191A (en) * | 2010-06-12 | 2010-12-22 | 华中农业大学 | Application of activated carbon modified material and application in removing arsenic from water |
| KR20110126300A (en) * | 2010-05-17 | 2011-11-23 | 한국화학연구원 | Visible-light photoactive spherical carbon porous material and its manufacturing method |
| CN102350352A (en) * | 2011-07-15 | 2012-02-15 | 浙江工业大学 | Preparation method of iron-doped TiO2 nanotube |
| WO2012139726A1 (en) * | 2011-04-14 | 2012-10-18 | Kronos International, Inc. | Process for producing a photocatalyst based on titanium dioxide |
-
2014
- 2014-12-09 CN CN201410749247.3A patent/CN104445575B/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1899686A (en) * | 2006-07-24 | 2007-01-24 | 同济大学 | Process for preparing iron blended TiO2/active carbon composite visible light catalyst |
| CN101219371A (en) * | 2007-01-08 | 2008-07-16 | 北京化工大学 | Photocatalysis oxidation treated high concentration organic trade waste |
| CN101565219A (en) * | 2008-04-25 | 2009-10-28 | 北京化工大学 | Process for photocatalytic treatment of industrial waste water |
| CN101628236A (en) * | 2009-08-03 | 2010-01-20 | 浙江理工大学 | Preparation method of kieselguhr load type compound photocatalyst with iron ions doped titanium dioxide |
| KR20110126300A (en) * | 2010-05-17 | 2011-11-23 | 한국화학연구원 | Visible-light photoactive spherical carbon porous material and its manufacturing method |
| CN101920191A (en) * | 2010-06-12 | 2010-12-22 | 华中农业大学 | Application of activated carbon modified material and application in removing arsenic from water |
| CN101905154A (en) * | 2010-08-20 | 2010-12-08 | 中国林业科学研究院林产化学工业研究所 | Method for improving efficiency of visible light response doping-type M-TiO2/AC photocatalyst |
| WO2012139726A1 (en) * | 2011-04-14 | 2012-10-18 | Kronos International, Inc. | Process for producing a photocatalyst based on titanium dioxide |
| CN102350352A (en) * | 2011-07-15 | 2012-02-15 | 浙江工业大学 | Preparation method of iron-doped TiO2 nanotube |
Non-Patent Citations (1)
| Title |
|---|
| 肖红艳等: "Fe~(3+)/TiO_2负载型活性炭的制备及其光催化活性的研究", 《印染》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106800321A (en) * | 2015-11-25 | 2017-06-06 | 湖南恒光化工有限公司 | A kind of process units that can process waste water |
| CN108017223A (en) * | 2016-11-03 | 2018-05-11 | 浙江水美环保工程有限公司 | A kind of steroid pharmacy wastewater treatment method |
| CN109368859A (en) * | 2018-11-15 | 2019-02-22 | 河南利华制药有限公司 | Upper fluorine waste water zero discharge treatment process in steroidal drug production |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104445575B (en) | 2016-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Al-Bsoul et al. | Optimal conditions for olive mill wastewater treatment using ultrasound and advanced oxidation processes | |
| CN102151567B (en) | Catalyst for oxidation and decomposition of organic pollutants in water with ozone and method thereof for catalyzing sewage treatment with ozone | |
| CN103145273B (en) | Method and device for adsorbing, reducing, oxidizing and degrading nitrobenzene wastewater | |
| CN103030208A (en) | Application of spinel ferrite catalyst and method for urging persulfate to generate free radicals to catalytically degrade organic matters | |
| Ginni et al. | Treatment of pulp and paper mill wastewater by solar photo-Fenton process | |
| Burbano et al. | Effect of oxidant-to-substrate ratios on the degradation of MTBE with Fenton reagent | |
| CN101638253B (en) | Method for treating waste water polluted by composite chlorophenol with coordination of visible light-laccase | |
| CN101774674A (en) | Method for processing organic wastewater by inorganic peroxide | |
| CN106976949A (en) | A kind of oxidation treatment method of Leachate site biological treatment water outlet | |
| Madhavan et al. | Kinetics of degradation of acid red 88 in the presence of Co2+-ion/peroxomonosulphate reagent | |
| CN107265788B (en) | A kind of industrial wastewater, exhaust treatment system | |
| Umamaheswari et al. | A feasibility study on optimization of combined advanced oxidation processes for municipal solid waste leachate treatment | |
| CN104445575B (en) | A kind of deep oxidation treatment process of steroid hormone medicine waste water | |
| CN101767859A (en) | Waste water treatment method combining Fenton oxidization and microwave catalysis phase | |
| CN103341358A (en) | Catalyst for treating chlorine-containing organic waste water, and preparation method thereof | |
| CN105536812A (en) | Nano Fe3O4/Mn3O4 composite material and preparation method and application thereof | |
| CN110127833A (en) | A kind of method that cupric reinforcing sulphite removes removal organic polluter with hydrogen peroxide system | |
| Sankara Narayanan et al. | Degradation of O-chlorophenol from aqueous solution by electro-Fenton process | |
| CN204981478U (en) | Leachate treatment system | |
| CN102432127A (en) | Advanced treatment system and method for biochemically hardly degradable organic wastewater | |
| CN104030429A (en) | Catalytic ozone oxidizing method for industrial wastewater deep treatment | |
| CN102285712B (en) | Method for removing micro pollutants from water by oxidization of potassium permanganate with ruthenium as catalyst | |
| CN106673171A (en) | Method for promoting peroxymonosulfate to generate sulfate radicals for degrading organic matters | |
| CN105568343B (en) | The methods and applications of ferriferous oxide ceramic film class fenton catalyst are prepared in titanium alloy surface using plasma electrolytic oxidation method | |
| CN114751559B (en) | Method for treating resin production wastewater based on combination of chemical precipitation and two-stage photocatalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160420 |